EP3974484A1 - Verwendung von vinylacetalen als bindemittel in drucktinten - Google Patents

Verwendung von vinylacetalen als bindemittel in drucktinten Download PDF

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Publication number
EP3974484A1
EP3974484A1 EP20198631.2A EP20198631A EP3974484A1 EP 3974484 A1 EP3974484 A1 EP 3974484A1 EP 20198631 A EP20198631 A EP 20198631A EP 3974484 A1 EP3974484 A1 EP 3974484A1
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EP
European Patent Office
Prior art keywords
ethylene vinyl
acetal
mol
ethylene
printing ink
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20198631.2A
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English (en)
French (fr)
Inventor
Michael Frank
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Europe GmbH
Original Assignee
Kuraray Europe GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Europe GmbH filed Critical Kuraray Europe GmbH
Priority to EP20198631.2A priority Critical patent/EP3974484A1/de
Priority to PCT/EP2021/075869 priority patent/WO2022063743A1/en
Priority to EP21777344.9A priority patent/EP4204502A1/de
Publication of EP3974484A1 publication Critical patent/EP3974484A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the invention is directed to the use of ethylene vinyl acetals as binder in printing inks.
  • polyvinyl acetals in particular polyvinyl butyrals
  • binders in printing ink formulations
  • polyvinyl acetals which exhibit minimal viscosity in solution are often used.
  • Such printing inks are widely used in the food packaging industry as almost all food packages are being printed on for information and advertising purposes.
  • Polyvinyl acetals and their use as binder in printing inks are expected to provide sufficient technical performance, especially the adhesion of the ink to the polymers OPP (oriented polypropylene) and PE (polyethylene), which are the most common substrates to be printed in the food industry, is critical and must have a minimum level. Therefore the addition of adhesion promoters is widely used and state of the art. On the other hand these adhesion promoters are typically non-polymeric materials and smaller molecules. They are often able to migrate from the ink into and through the different layers of the packaging material and in worse case scenarios they can have finally direct contact with foodstuffs. As safety requirements in the food industry are becoming more and more stringent such scenarios shall be avoided.
  • one objective of the invention is to provide printing ink binders with improved adhesion, improved compatibility and barrier properties, with an improved environmental and safety impact and/or with a better economical profile in the production and use of the printing ink.
  • ethylene vinyl acetals with a rather high ethylene content not only lead to an improved compatibility to the polymers OPP (oriented polypropylene) and PE (polyethylene), and thus, leading to an improved adhesion of the printing inks comprising these as a binder.
  • these acetalized ethylene vinyl alcohols (EVOH) keep the well-known oxygen barrier properties of the non-acetalized starting material EVOH.
  • using the ethylene vinyl acetals according to this invention leads to an improvement in the printing process itself while adding an oxygen barrier, which is basically absent from materials like the substrates PE and OPP as well as the commonly used binder PVB.
  • the present invention concerns the use of an ethylene vinyl acetal as a binder in printing ink formulations wherein the ethylene vinyl acetal comprises ethylene units in the range of 25 to 60 mol%.
  • the ethylene vinyl acetal of the present invention can be obtained by subjecting an aldehyde to an acetalization reaction with an ethylene vinyl alcohol (EVOH).
  • EVOH ethylene vinyl alcohol
  • Such ethylene vinyl alcohols are known in the art and can be obtained by copolymerizing ethylene in the presence of an acidic catalyst. Furthermore, ethylene vinyl alcohols are commercially available.
  • the ethylene vinyl alcohol is obtained by copolymerizing ethylene and a vinyl acetate and hydrolysing the obtained copolymer.
  • a conventionally known alkali catalyst or an acid catalyst can be used and among them, a hydrolysation reaction using methanol as a solvent and caustic soda (NaOH) catalyst is convenient.
  • the percentage of ethylene units in the ethylene vinyl alcohol is 25 to 60 mol%, more preferably 30 to 55 mol%, and still more preferably 35 to 50 mol%.
  • the reaction product obtained after the acetalization reaction is neutralized with alkali, and then washed with water to obtain the ethylene vinyl acetal.
  • the catalyst for carrying out the acetalization reaction is not particularly limited, and any organic acid or inorganic acid may be used. Examples thereof include acetic acid, para toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, carbonic acid, and the like.
  • the degree of saponification of the acetate groups is preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, and most preferably 99.9 mol% or more.
  • the percentage of ethylene units in the ethylene vinyl acetal is 30 to 55 mol%, and more preferably 35 to 50 mol%. Also preferably, the percentage of ethylene units in the ethylene vinyl acetal is from 50 to 60 mol%.
  • the acetal groups individually have 1 to 7 carbon atoms, i.e. they derive from the condensation reaction with aldehydes with 1 to 7 carbon atoms. More preferably, they derive from the list consisting of methanal (formaldehyde), acetaldehyde, n-propanal (propionaldehyde), n-butanal (butyraldehyde), iso-butanal (2-methyl-1-propanal, iso-butyraldehyde), n-pentanal (valeraldeyhde), iso-pentanal (3-methyl-1-butanal), sec-pentanal (2-methyl-1-butanal), tert-pentanal (2,2,dimethyl-1-propanal), n-hexanal (capronaldehyde), iso-hexanal (2-methyl-1-pentanal, 3-methyl-1-pentanal, 4-methyl-1-pentanal), 2,2-di
  • the ethylene vinyl acetals used in the inventive process are mixed acetals, i.e. they comprise at least two different acetal groups.
  • the ethylene vinyl acetals as used in the invention comprise a first acetal group derived from the reaction of two hydroxyl groups of the respective ethylene vinyl alcohol with one aldehyde and at least a second acetal group derived from the reaction of two other hydroxyl groups of the respective ethylene vinyl alcohol with a second aldehyde, wherein the first aldehyde is different from the second aldehyde.
  • the preferred aldehydes are the same as used for the acetals with one acetal group as listed above; the most preferable combination is a mixture of acetals derived from acetaldehyde and n-butyraldehyde.
  • the method for producing the ethylene vinyl acetals used in this embodiment of the present invention can be produced by a method in which an aldehyde is added to an ethylene vinyl alcohol solution under acidic conditions and subjected to an acetalization reaction.
  • the degree of acetalization of the ethylene vinyl acetal used in the present invention is 5 mol% or more and less than 40 mol%, more preferably the lower limit of the degree of acetalization is more than 6 mol%, more than 7 mol%, more than 8 mol%, more than 9 mol%, and most preferably more than 10 mol%.
  • the upper limit of the degree of acetalization is more preferably 38 mol% or less, 36 mol% or less, 34 mol% or less, and 32 mol% or less in this order, and most preferably less than 30 mol%.
  • the percentage of vinyl alcohol units in the ethylenevinyl acetal resin of the present invention is 24 to 71 mol% based on the total monomer unit constituting the resin.
  • the vinyl alcohol content and vinyl acetate content of ethylene vinyl acetals were determined in accordance with DIN ISO 3681 (Acetate content) and DIN ISO 53240 (PVA content).
  • the vinyl acetal content is calculated as the remaining portion from the sum of vinyl alcohol content and vinyl acetate content determined in accordance with DIN ISO 53401/53240 and the ethylene needed to make one hundred.
  • the degree of acetalisation is calculated from the amount of vinyl acetal content divided by the sum of vinyl alcohol content, vinyl acetal content and vinyl acetate content. Conversion from % by weight into mol % is achieved by formulas known to the person skilled in the art.
  • the ethylene content of the ethylene vinyl acetate copolymer is measured by NMR spectroscopy.
  • the ethylene vinyl acetal resin is dissolved in ethanol and a 2 N hydrochloride hydroxylamine solution and hydrochloric acid are added, and the mixture is stirred under reflux with a condenser in a water bath for 4 hours, and after cooling, ammonia water is added.
  • methanol is added and the polymer is precipitated, washed and dried to obtain the acetylated ethylene vinyl alcohol copolymer.
  • acetylated ethylene vinyl alcohol copolymer is dissolved in DMSO (dimethyl sulfoxide) at 120 °C, cooled to room temperature, and then N,N-dimethyl-4-aminopyridine and acetic anhydride are added thereto, followed by stirring for 1 h, followed by precipitation with ion-exchanged water and acetone, and drying to obtain an ethylene vinyl acetate copolymer.
  • DMSO dimethyl sulfoxide
  • N,N-dimethyl-4-aminopyridine and acetic anhydride are added thereto, followed by stirring for 1 h, followed by precipitation with ion-exchanged water and acetone, and drying to obtain an ethylene vinyl acetate copolymer.
  • the polymer is dissolved in DMSO-d6 and measured by a proton NMR spectrometer of 400 MHz. The spectrum obtained was integrated 256 times.
  • the molar ratio of the ethylene unist of the ethylene vinyl alcohol copolymer is calculated from the intensity ratio of the methine proton (peak of 1.1 to 1.9 ppm) derived from the ethylene unit and the vinyl acetate unit, and the terminal methyl proton (peak of 2.0ppm) derived from the vinyl acetate unit. Note that, since the ethylene unit is not affected by the acetalization reaction, the molar ratio (n) of the ethylene unit of the ethylene vinyl alcohol copolymer before the acetalization reaction is equal to the molar ratio (n) of the ethylene unit of the ethylene vinyl acetal resin obtained after the acetalization reaction.
  • the present invention concerns a printing ink comprising an ethylene vinyl acetal as a binder wherein the ethylene vinyl acetal comprises ethylene units in the range of 25 to 60 mol%.
  • the acetal group has 2 to 7 carbon atoms and is derived from the same aldehyde(s) as described above.
  • the ethylene vinyl acetal comprises n-butylaldehyde and/or acetaldehyde acetal groups.
  • the printing ink comprises a co-binders.
  • Suitable co-binders include polyurethanes (PU), nitrocellulose (NC), polyamides (PA) and mixtures thereof.
  • the co-binder is polyurethane and/or nitrocellulose.
  • the printing ink may comprise other components chosen inter alia from colorants, for example insoluble organic and/or inorganic pigments or soluble dyes, especially organic pigments like PY13, PR57:1; PB15:3; PG7, PB61, PV23, titanium dioxide, carbon black, metallic effect pigments, e.g. powdered aluminum or brass, and additives like fillers, e.g.
  • colorants for example insoluble organic and/or inorganic pigments or soluble dyes, especially organic pigments like PY13, PR57:1; PB15:3; PG7, PB61, PV23, titanium dioxide, carbon black, metallic effect pigments, e.g. powdered aluminum or brass, and additives like fillers, e.g.
  • kaolin or chalk acid catalysts, adhesion promoters, amine solubiliser, antifoam agents, biocides, dispersing agents, flow agents, jellifying agents, inhibitors, ink stabilisers, optical brighteners, photoinitiators, siccative agents, slip agents, suspension agents, plasticizer, thickeners, UV stabilisers, waxes, and/or wetting agents.
  • the material used for the inventive process can also comprise other polymers different from the ethylene vinyl acetals described above. It can comprise one or more other ethylene vinyl acetal grades, differing in hydroxyl content and/or degree of polymerization and/or degree of acetate content and/or type of acetal and/or in ethylene content.
  • Methods for coating a substrate with the printing ink of the invention include well-known methods such as direct coating and printing.
  • methods including curtain coating, flow coating and roll coating can be used.
  • direct coating such as spray coating can also be employed.
  • Printing processes used for coating include offset printing, gravure offset printing, and gravure and flexographic printing processes.
  • the thickness of the coating film produced by these processes can be 0.25 to 25 micrometers, and typically, 1 to 10 micrometers.
  • Substrates may include paper, wood, plastic, or textiles.
  • printing inks of the invention may be applied to paper and films or sheets of polyethylene, polyvinyl chloride, polypropylene, polyester, polycarbonate, and polyamide, and paper treated with any of these materials.
  • the substrate may preferably be pre-treated for a better coating or printing result, e.g. by corona treatment known in the art.
  • the substrate coated or printing with the ink composition is generally laminated to protect it.
  • the lamination is carried out by procedures well known to a person skilled in the art. Laminates in general are obtained for example by applying the ink-formulation to surface of a plastic substrate. After drying, a coated substrate is obtained. Subsequently a lamination adhesive is used to fix a second plastic surface to the coated substrate.
  • the ethylene vinyl acetal thus obtained has a content of ethylene units of 44 mol% and an acetalization degree of 31 mol% and is subsequently used to prepare a printing ink as described above.
  • the printing ink thus produced was used in the printing process as described above. The engineering properties are measured on the resulting specimen.
  • the ethylene vinyl acetal thus obtained has a content of ethylene units of 44 mol% and an acetalization degree of 55 mol% and is subsequently used to prepare a printing ink as described above.
  • the printing ink thus produced was used in the printing process as described above. The engineering properties are measured on the resulting specimen.
  • the printing ink thus produced is used in the printing process as described above.
  • the engineering properties are measured on the resulting specimen.
  • the printing ink is prepared as follows: 44.2 g ethylene vinyl acetal or polyvinyl acetal (for comparative example) are dissolved in 208.4 g ethanol at room temperature. Subsequently, 88.8 g Irgalite ® Blue GLO (pigment available from BASF SE) is added. The resulting mixture is dispersed using a Getzmann Dispermat ® , model CA 40-C, with the following settings:
  • the pigment concentrate is separated from the glass beads on a filter.
  • 72 g of the pigment concentrate are taken and this initial charge is diluted with a 20% strength by weight solution of the respective ethylene vinyl acetal (or polyvinyl acetal) in ethanol until the printing ink has a fixed pigment to ethylene vinyl acetal (or to polyvinyl acetal) ratio of 1:1.7.
  • polyethyleneimine product as adhesion promoter Lupasol WF (trademark of BASF, Ludwigshafen) with 0.75%.
  • the ink is applied on the treated side (corona technique) of a coextruded OPP film (Oriented Polypropylene Film, obtained from Mitsubishi Chemicals) using a small lab gravure printer (Labratester 180 from Norbert Schläfli Maschinen).
  • the inks are applied as a single layer.
  • the resulting prints are dried at room temperature over a period of about 16 hours, before making a laminate.
  • the coextruded OPP films with the printed inks prepared above are laminated to a second coextruded OPP film using a polyurethane adhesive to give OPP/OPP laminates according to the following procedure.
  • a 2-component polyurethane lamination adhesive is prepared by mixing Morchem Hardener CS-90 (3.25 g, obtained from MORCHEM GmbH, Germany), Morchem PS 246 A (50.0 g, obtained from MORCHEM GmbH, Germany) and ethyl acetate (54.8 g).
  • the freshly prepared adhesive is applied to the second (unprinted) film at a coating weight of 3.0 g/m 2 (dry), and subsequently dried in the oven for 45s at 80°C to evaporate the solvent.
  • the printed film is then carefully applied with the printed side to the adhesive print, thereby avoiding creation of air bubbles in the laminate.
  • the resulting laminates are stored for 3 days under pressure, in order to allow the adhesive to cure.
  • a number of 5 strips with a width of 15 ⁇ 0,1 mm are cut from the cured laminate and the lamination bond strength is tested in a peel test using a tensile testing machine. Measurement is done at a speed of 150 mm/min. The peeling path is at least 20 mm.
  • the laminated stripe is kept under a constant 90° angle against the film clamps. Measurements are done according to DIN 53357. Sample preparation is in accordance with DIN 16906. The results of the tests show that the laminates prepared with the ethylene vinyl acetals lead to an improved performance, e.g. in the number of OPP film breakage (marked with "B") as opposed to laminate failure caused by peeling the laminate (marked with "P").
  • the breakage of the OPP film indicates that the lamination strength with the binder / ink system is higher than the tensile strength of the OPP film itself, indicating a very good performance of the PVB comparison as an ink binder.
  • the results show that the laminates obtained using an ethylene vinyl acetal as a binder give better performance even without an adhesion promoter.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP20198631.2A 2020-09-28 2020-09-28 Verwendung von vinylacetalen als bindemittel in drucktinten Withdrawn EP3974484A1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20198631.2A EP3974484A1 (de) 2020-09-28 2020-09-28 Verwendung von vinylacetalen als bindemittel in drucktinten
PCT/EP2021/075869 WO2022063743A1 (en) 2020-09-28 2021-09-21 Use of ethylene vinyl acetals as binder in printing inks
EP21777344.9A EP4204502A1 (de) 2020-09-28 2021-09-21 Verwendung von ethylenvinylacetalen als bindemittel in druckfarben

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20198631.2A EP3974484A1 (de) 2020-09-28 2020-09-28 Verwendung von vinylacetalen als bindemittel in drucktinten

Publications (1)

Publication Number Publication Date
EP3974484A1 true EP3974484A1 (de) 2022-03-30

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP20198631.2A Withdrawn EP3974484A1 (de) 2020-09-28 2020-09-28 Verwendung von vinylacetalen als bindemittel in drucktinten
EP21777344.9A Pending EP4204502A1 (de) 2020-09-28 2021-09-21 Verwendung von ethylenvinylacetalen als bindemittel in druckfarben

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP21777344.9A Pending EP4204502A1 (de) 2020-09-28 2021-09-21 Verwendung von ethylenvinylacetalen als bindemittel in druckfarben

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EP (2) EP3974484A1 (de)
WO (1) WO2022063743A1 (de)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8470908B2 (en) * 2010-07-21 2013-06-25 Kuraray Europe Gmbh Use of polymer isoacetals in printing ink formulations
EP2933278A1 (de) * 2014-04-17 2015-10-21 Agfa Graphics Nv (Ethylen-,Vinylacetal-)Copolymere und ihre Verwendung in Lithographiedruckplattenvorläufern
EP2944657A1 (de) * 2014-05-15 2015-11-18 Agfa Graphics Nv (Ethylen-,Vinylacetal-)Copolymere und deren Verwendung in Lithographiedruckplattenvorläufern
EP2963496A1 (de) * 2014-06-30 2016-01-06 Agfa Graphics Nv Lithografiedruckplattenvorläufer mit (Ethylen-, Vinylacetal-)Copolymeren
JP2016028139A (ja) 2014-07-11 2016-02-25 株式会社クラレ エチレン−ビニルアルコール共重合体、樹脂組成物、及び多層構造体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8470908B2 (en) * 2010-07-21 2013-06-25 Kuraray Europe Gmbh Use of polymer isoacetals in printing ink formulations
EP2933278A1 (de) * 2014-04-17 2015-10-21 Agfa Graphics Nv (Ethylen-,Vinylacetal-)Copolymere und ihre Verwendung in Lithographiedruckplattenvorläufern
EP2944657A1 (de) * 2014-05-15 2015-11-18 Agfa Graphics Nv (Ethylen-,Vinylacetal-)Copolymere und deren Verwendung in Lithographiedruckplattenvorläufern
EP2963496A1 (de) * 2014-06-30 2016-01-06 Agfa Graphics Nv Lithografiedruckplattenvorläufer mit (Ethylen-, Vinylacetal-)Copolymeren
JP2016028139A (ja) 2014-07-11 2016-02-25 株式会社クラレ エチレン−ビニルアルコール共重合体、樹脂組成物、及び多層構造体

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Publication number Publication date
EP4204502A1 (de) 2023-07-05
WO2022063743A1 (en) 2022-03-31

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